Method for producing water-absorbing polymer particles by suspension polymerization

ABSTRACT

A process for producing water-absorbing polymer particles by suspension polymerization and thermal surface postcrosslinking, wherein the agglomerated base polymer obtained by suspension polymerization has a centrifuge retention capacity of at least 37 g/g and the thermal surface postcrosslinking is conducted at 100 to 190° C.

The present invention relates to a process for producing water-absorbingpolymer particles by suspension polymerization and thermal surfacepostcrosslinking, wherein the agglomerated base polymer obtained bysuspension polymerization has a centrifuge retention capacity of atleast 37 g/g and the thermal surface postcrosslinking is conducted at100 to 190° C.

The production of water-absorbing polymer particles is described in themonograph “Modern Superabsorbent Polymer Technology”, F. L. Buchholz andA. T. Graham, Wiley-VCH, 1998, pages 69 to 117. The water-absorbingpolymer particles are typically produced by solution polymerization orsuspension polymerization.

Being products which absorb aqueous solutions, water-absorbing polymersare used to produce diapers, tampons, sanitary napkins and other hygienearticles, but also as water-retaining agents in market gardening.

The properties of the water-absorbing polymers can be adjusted via thelevel of crosslinking. With increasing level of crosslinking, there is arise in gel strength and a fall in absorption capacity.

To improve the use properties, for example permeability in the swollengel bed in the diaper and absorption under pressure, water-absorbingpolymer particles are generally surface postcrosslinked. This increasesonly the level of crosslinking of the particle surface, and in this wayit is possible to at least partly decouple absorption under pressure andcentrifuge retention capacity.

JP S63-218702 describes a continuous process for producingwater-absorbing polymer particles by suspension polymerization.

WO 2006/014031 A1 describes a process for producing water-absorbingpolymer particles by suspension polymerization. At the high temperaturesin the thermal postcrosslinking, the fraction of hydrophobic solvent isdriven out.

WO 2008/068208 A1 likewise relates to a process for producingwater-absorbing polymer particles having a low proportion of hydrophobicsolvents by suspension polymerization.

It was an object of the present invention to provide an improved processfor producing water-absorbing polymer particles by suspensionpolymerization, wherein the water-absorbing polymer particles shouldhave a high centrifuge retention capacity (CRC), a high absorption undera pressure of 49.2 g/cm² (AUHL), a high sum total of centrifugeretention capacity (CRC) and absorption under a pressure of 49.2 g/cm²(AUHL), and a low level of extractables.

The object was achieved by a process for producing water-absorbingpolymer particles by polymerizing a monomer solution comprising

a) at least one ethylenically unsaturated monomer which bears acidgroups and may have been at least partly neutralized,

b) optionally one or more crosslinkers,

c) at least one initiator,

d) optionally one or more ethylenically unsaturated monomerscopolymerizable with the monomers mentioned under a) and

e) optionally one or more water-soluble polymers,

the monomer solution suspended in a hydrophobic organic solvent duringthe polymerization being agglomerated during or after the polymerizationin the hydrophobic organic solvent, and thermally surfacepostcrosslinking the resultant agglomerated polymer particles by meansof an organic surface postcrosslinker, wherein the amount of crosslinkerb) is selected such that the agglomerated polymer particles before thesurface postcrosslinking have a centrifuge retention capacity of atleast 37 g/g and the thermal surface postcrosslinking is conducted at100 to 190° C.

In a preferred embodiment of the present invention, the amount ofcrosslinker b) is selected such that the agglomerated polymer particles,prior to the surface postcrosslinking, have a centrifuge retentioncapacity of at least 38 g/g, and the thermal surface postcrosslinking isconducted at 105 to 180° C.

In a particularly preferred embodiment of the present invention, theamount of crosslinker b) is selected such that the agglomerated polymerparticles, prior to the surface postcrosslinking, have a centrifugeretention capacity of at least 39 g/g, and the thermal surfacepostcrosslinking is conducted at 110 to 175° C.

In a very particularly preferred embodiment of the present invention,the amount of crosslinker b) is selected such that the agglomeratedpolymer particles, prior to the surface postcrosslinking, have acentrifuge retention capacity of at least 40 g/g, and the thermalsurface postcrosslinking is conducted at 120 to 170° C.

The monomers a) are preferably water-soluble, i.e. the solubility inwater at 23° C. is typically at least 1 g/100 g of water, preferably atleast 5 g/100 g of water, more preferably at least 25 g/100 g of waterand most preferably at least 35 g/100 g of water.

Suitable monomers a) are, for example, ethylenically unsaturatedcarboxylic acids, such as acrylic acid, methacrylic acid and itaconicacid. Particularly preferred monomers are acrylic acid and methacrylicacid. Very particular preference is given to acrylic acid.

Further suitable monomers a) are, for example, ethylenically unsaturatedsulfonic acids, such as styrenesulfonic acid and2-acrylamido-2-methylpropanesulfonic acid (AMPS).

Impurities can have a considerable influence on the polymerization. Theraw materials used should therefore have a maximum purity. It istherefore often advantageous to specially purify the monomers a).Suitable purification processes are described, for example, in WO2002/055469 Al1 WO 2003/078378 A1 and WO 2004/035514 A1. A suitablemonomer a) is, for example, an acrylic acid purified according to WO2004/035514 A1 and comprising 99.8460% by weight of acrylic acid,0.0950% by weight of acetic acid, 0.0332% by weight of water, 0.0203% byweight of propionic acid, 0.0001% by weight of furfurals, 0.0001% byweight of maleic anhydride, 0.0003% by weight of diacrylic acid and0.0050% by weight of hydroquinone monomethyl ether.

The proportion of acrylic acid and/or salts thereof in the total amountof monomers a) is preferably at least 50 mol %, more preferably at least90 mol %, most preferably at least 95 mol %.

The acid groups of the monomers a) may have been partly neutralized. Theneutralization is conducted at the monomer stage. This is typicallyaccomplished by mixing in the neutralizing agent as an aqueous solutionor else preferably as a solid. The degree of neutralization ispreferably from 25 to 95 mol %, more preferably from 30 to 80 mol % andmost preferably from 40 to 75 mol %, for which the customaryneutralizing agents can be used, preferably alkali metal hydroxides,alkali metal oxides, alkali metal carbonates or alkali metalhydrogencarbonates and also mixtures thereof. Instead of alkali metalsalts, it is also possible to use ammonium salts.

Particularly preferred alkali metals are sodium and potassium, but veryparticular preference is given to sodium hydroxide, sodium carbonate orsodium hydrogencarbonate and also mixtures thereof.

The monomers a) typically comprise polymerization inhibitors, preferablyhydroquinone monoethers, as storage stabilizers.

The monomer solution comprises preferably up to 250 ppm by weight,preferably at most 130 ppm by weight, more preferably at most 70 ppm byweight, and preferably at least 10 ppm by weight, more preferably atleast 30 ppm by weight and especially around 50 ppm by weight, ofhydroquinone monoether, based in each case on the unneutralized monomera). For example, the monomer solution can be prepared by using anethylenically unsaturated monomer bearing acid groups with anappropriate content of hydroquinone monoether.

Preferred hydroquinone monoethers are hydroquinone monomethyl ether(MEHQ) and/or alpha-tocopherol (vitamin E). Suitable crosslinkers b) arecompounds having at least two groups suitable for crosslinking. Suchgroups are, for example, ethylenically unsaturated groups which can bepolymerized free-radically into the polymer chain, and functional groupswhich can form covalent bonds with the acid groups of the monomer a). Inaddition, polyvalent metal salts which can form coordinate bonds with atleast two acid groups of the monomer a) are also suitable ascrosslinkers b).

Crosslinkers b) are preferably compounds having at least twopolymerizable groups which can be polymerized free-radically into thepolymer network. Suitable crosslinkers b) are, for example,methylenebisacrylamide, ethylene glycol dimethacrylate, diethyleneglycol diacrylate, polyethylene glycol diacrylate, allyl methacrylate,trimethylolpropane triacrylate, triallylamine, tetraallylammoniumchloride, tetraallyloxyethane, as described in EP 0 530 438 A1, di- andtriacrylates, as described in EP 0 547 847 A1, EP 0 559 476 A1, EP 0 632068 A1, WO 93/21237 A1, WO 2003/104299 A1, WO 2003/104300 A1, WO2003/104301 A1 and DE 103 31 450 Al, mixed acrylates which, as well asacrylate groups, comprise further ethylenically unsaturated groups, asdescribed in DE 103 31 456 A1 and DE 103 55 401 A1, or crosslinkermixtures, as described, for example, in DE 195 43 368 A1, DE 196 46 484A1, WO 90/15830 A1 and WO 2002/032962 A2.

Preferred crosslinkers b) are pentaerythrityl triallyl ether,tetraallyloxyethane, methylenebismethacrylamide, 15-tuply ethoxylatedtrimethylolpropane triacrylate, polyethylene glycol diacrylate,trimethylolpropane triacrylate and triallylamine.

Very particularly preferred crosslinkers b) are methylenebisacrylamideand the polyethoxylated and/or -propoxylated glycerols which have beenesterified with acrylic acid or methacrylic acid to give di- ortriacrylates, as described, for example, in WO 2003/104301 A1.

Methylenebisacrylamide and di- and/or triacrylates of 3- to 10-tuplyethoxylated glycerol are particularly advantageous. Very particularpreference is given to methylenebisacrylamide, di- or triacrylates of 1-to 5-tuply ethoxylated and/or propoxylated glycerol. Most preferred aremethylenebisacrylamide and the triacrylates of 3- to 5-tuply ethoxylatedand/or propoxylated glycerol, especially methylenebisacrylamide and thetriacrylate of 3-tuply ethoxylated glycerol.

The amount of crosslinker in the monomer solution is selected such thatthe water-absorbing polymer particles after the polymerization andbefore the thermal surface postcrosslinking (base polymer) have acentrifuge retention capacity (CRC) of at least 37 g/g, preferably atleast 38 g/g, more preferably at least 39 g/g, most preferably at least40 g/g. The centrifuge retention capacity (CRC) should not exceed 75g/g. If the centrifuge retention capacity (CRC) of the base polymer istoo high, it is not possible to build up sufficient absorption under apressure of 49.2 g/cm² (AUHL) in the subsequent thermal surfacepostcrosslinking.

Initiators c) used may be all compounds which generate free radicalsunder the polymerization conditions, for example thermal initiators,redox initiators or photoinitiators. Suitable redox initiators arepotassium peroxodisulfate or sodium peroxodisulfate/ascorbic acid,hydrogen peroxide/ascorbic acid, potassium peroxodisulfate or sodiumperoxodisulfate/sodium bisulfite and hydrogen peroxide/sodium bisulfite.Preference is given to using mixtures of thermal initiators and redoxinitiators, such as potassium peroxodisulfate or sodiumperoxodisulfate/hydrogen peroxide/ascorbic acid. The reducing componentused is, however, preferably a mixture of the sodium salt of2-hydroxy-2-sulfinatoacetic acid, the disodium salt of2-hydroxy-2-sulfonatoacetic acid and sodium bisulfite. Such mixtures areobtainable as Brüggolite® FF6 and Brüggolite® FF7 (Bruggemann Chemicals;Heilbronn; Germany).

Suitable thermal initiators are especially azo initiators, such as2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride and2,2′-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride,2,2″-azobis(2-amidinopropane) dihydrochloride,4,4″-azobis(4-cyanopentanoic acid), 4,4′ and the sodium salts thereof,2,2″-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] and2,2′-azobis(imino-1-pyrrolidino-2-ethylpropane) dihydrochloride.

Suitable photoinitiators are, for example,2-hydroxy-2-methylpropiophenone and1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one.

Ethylenically unsaturated monomers d) copolymerizable with theethylenically unsaturated monomers a) bearing acid groups are, forexample, acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethylmethacrylate, dimethylaminoethyl methacrylate, dimethylaminoethylacrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate,dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate.

The water-soluble polymers e) used may be polyvinyl alcohol,polyvinylpyrrolidone, starch, starch derivatives, modified cellulose,such as methyl cellulose or hydroxyethyl cellulose, gelatin, polyglycolsor polyacrylic acids, preferably starch, starch derivatives and modifiedcellulose.

Optionally, one or more chelating agents may be added to the monomersolution or starting materials thereof to mask metal ions, for exampleiron, for the purpose of stabilization. Suitable chelating agents are,for example, alkali metal citrates, citric acid, alkali metal tartrates,pentasodium triphosphate, ethylenediamine tetraacetate, nitrilotriaceticacid, and also all chelating agents known by the Trilon® name, forexample Trilon® C (pentasodium diethylenetriaminepentaacetate), Trilon®D (trisodium (hydroxyethyl)ethylenediaminetriacetate), and Trilon® M(methylglycinediacetic acid).

For optimal action, the preferred polymerization inhibitors requiredissolved oxygen. The monomer solution can therefore be freed ofdissolved oxygen before the polymerization by inertization, i.e. flowingan inert gas through, preferably nitrogen or carbon dioxide. If thepolymerization is conducted under adequate reflux, the inertization canbe dispensed with. In this case, the dissolved oxygen is removed fromthe polymerization reactor together with the evaporating solvent.

For polymerization, the monomer solution is suspended or emulsified in ahydrophobic solvent.

Usable hydrophobic solvents are all the solvents known to the personskilled in the art for use in suspension polymerization. Preference isgiven to using aliphatic hydrocarbons, such as n-hexane, n-heptane,n-octane, n-nonane, n-decane, cyclohexane or mixtures thereof.Hydrophobic solvents have a solubility in water at 23° C. of less than 5g/100 g, preferably less than 1 g/100 g, more preferably less than 0.5g/100 g.

The hydrophobic solvent boils within the range from preferably 50 to150° C., more preferably 60 to 120° C., most preferably 70 to 90° C.

The ratio between hydrophobic solvent and monomer solution is 0.2 to3.0, preferably 0.3 to 2.7 and very preferably from 0.4 to 2.4.

For dispersion of the aqueous monomer solution in the hydrophobicsolvent or for dispersion of the water-absorbing polymer particles whichform, it is possible to add dispersing aids. These dispersing aids maybe anionic, cationic, nonionic or amphoteric surfactants, or natural,semisynthetic or synthetic polymers.

Anionic surfactants are, for example, sodium polyoxyethylene dodecylether sulfate and sodium dodecyl ether sulfate. A cationic surfactantis, for example, trimethylstearylammonium chloride. An amphotericsurfactant is, for example, carboxymethyldimethylcetylammonium. Nonionicsurfactants are, for example, sucrose fatty acid esters, such as sucrosemonostearate and sucrose dilaurate, sorbitan esters such as sorbitanmonostearate, trehalose fatty acid esters, such as trehalose stearate,polyoxyalkylene compounds based on sorbitan esters, such aspolyoxyethylenesorbitan monostearate.

Suitable polymers are, for example, cellulose derivatives such ashydroxyethyl cellulose, methyl hydroxyethyl cellulose, methylhydroxypropyl cellulose, methyl cellulose and carboxymethyl cellulose,polyvinylpyrrolidone, copolymers of vinylpyrrolidone, gelatin, gumarabic, xanthan, casein, polyglycerols, polyglycerol fatty acid esters,polyethylene glycols, modified polyethylene glycol such as polyethyleneglycol stearate or polyethylene glycol stearyl ether stearate, polyvinylalcohol, partially hydrolyzed polyvinyl acetates and modifiedpolyethylene, such as a maleic acid-modified polyethylene.

It is also possible to use inorganic particles as dispersing aids, thesebeing called Pickering systems. Such a Pickering system may consist ofthe solid particles on their own or additionally of auxiliaries whichimprove the dispersibility of the particles in water or the wettabilityof the particles by the hydrophobic solvent. The way in which they workand their use are described in WO 99/24525 A1 and EP 1 321 182 A1.

The inorganic solid particles may be metal salts, such as salts, oxidesand hydroxides of calcium, magnesium, iron, zinc, nickel, titanium,aluminum, silicon, barium and manganese.

These include magnesium hydroxide, magnesium carbonate, magnesium oxide,calcium oxalate, calcium carbonate, barium carbonate, barium sulfate,titanium dioxide, aluminum oxide, aluminum hydroxide and zinc sulfide.These likewise include silicates, bentonite, hydroxyapatite andhydrotalcites. Particular preference is given to SiO₂-based silicas,magnesium pyrophosphate and tricalcium phosphate.

Suitable SiO₂-based dispersing aids are finely divided silicas. Thesecan be dispersed in water as fine solid particles. It is also possibleto use what are called colloidal dispersions of silica in water. Suchcolloidal dispersions are alkaline aqueous mixtures of silica. In thealkaline pH range, the particles are swollen and stable in water.Preferred colloidal dispersions of silica, at pH 9.3, have a specificsurface area in the range from 20 to 90 m²/g.

In addition, it is possible to use any desired mixtures of thedispersing aids.

The dispersing aid is typically dissolved or dispersed in thehydrophobic solvent. The dispersing aid is used in amounts between 0.01and 10% by weight, preferably between 0.2 and 5% by weight, morepreferably between 0.5 and 2% by weight, based on the monomer solution.The diameter of the monomer solution droplets can be adjusted via thetype and amount of dispersing aid.

The diameter of the monomer solution droplets can be adjusted via thestirrer energy introduced and through suitable dispersing aids.

The performance of the agglomeration is known to those skilled in theart and is not subject to any restrictions. The polymerization and theagglomeration can be conducted simultaneously (one-stage metering) orsuccessively (two-stage metering).

In the case of one-stage metering, the monomer solution is metered intothe hydrophobic solvent and the droplets of monomer solution agglomerateduring the polymerization.

In the case of two-stage metering, a first monomer solution is firstmetered into the hydrophobic solvent and the droplets of monomersolution are polymerized. Then a second monomer solution is metered intothe dispersed polymer particles thus obtained and polymerization iseffected again. The polymer particles do not agglomerate until thesecond polymerization. The first and second monomer solutions may beidentical or different in terms of composition. With every furtheraddition of monomer to agglomerates that have already formed,irrespective of whether they have been prepared by one-stage ortwo-stage metering, the agglomerates can be agglomerated further to givelarger agglomerates.

There may be cooling steps between the metered additions of monomer.Some of the dispersing aid may precipitate out therein.

Whether the droplets of the monomer solution agglomerate or not duringthe polymerization can be established via the type and amount of thedispersing aid. Given a sufficient amount of dispersing aid,agglomeration during the polymerization of the droplets of monomersolution is prevented. The amount necessary for this purpose depends onthe type of dispersing aid.

Preference is given to two-stage metered addition, i.e. agglomerationafter the polymerization of the droplets of monomer solution.

Advantageously, several stirred reactors are connected in series for thepolymerization. Through postreaction in further stirred reactors, themonomer conversion can be increased and backmixing can be reduced. Inthis context, it is additionally advantageous when the first stirredreactor is not too large. With increasing size of the stirred reactor,there is inevitably broadening of the size distribution of the dispersedmonomer solution droplets. A relatively small first reactor thereforeenables the production of water-absorbing polymer particles with aparticularly narrow particle size distribution.

The reaction is preferably conducted under reduced pressure, for exampleat a pressure of 800 mbar. The pressure can be used to set the boilingpoint of the reaction mixture to the desired reaction temperature.

In a preferred embodiment of the present invention, the polymerizationis conducted in the presence of a typically water-soluble chain transferreagent.

Chain transfer reagents intervene in the polymerization kinetics andcontrol the molar mass. Suitable chain transfer reagents are thiols,thiol acids, secondary alcohols, phosphorus compounds, lactic acid,aminocarboxylic acids, etc.

The chain transfer reagent is used in an amount of preferably 0.00001 to0.1 mol/mol, more preferably of 0.00015 to 0.08 mol/mol, most preferably0.0002 to 0.06 mol/mol, based in each case on the monomer a).

The resultant water-absorbing polymer particles are thermally surfacepostcrosslinked. The thermal surface postcrosslinking can be conductedin the polymer dispersion or with the water-absorbing polymer particleswhich have been removed from the polymer dispersion and dried. Additionof the monomer solution may also be above the boiling point of water orof the solvent or the solvent/water azeotrope, such that solvent or asolvent/water azeotrope is distilled off continuously during theaddition of monomer.

In a preferred embodiment of the present invention, the water-absorbingpolymer particles are dewatered azeotropically in the polymer dispersionand filtered out of the polymer dispersion, and the filteredwater-absorbing polymer particles are dried to remove the adheringresidual hydrophobic solvent and thermally surface postcrosslinked.

Suitable surface postcrosslinkers are compounds which comprise groupswhich can form covalent bonds with at least two carboxylate groups ofthe polymer particles. Suitable compounds are, for example,polyfunctional amines, polyfunctional amido amines, polyfunctionalepoxides, as described in EP 0 083 022 A2, EP 0 543 303 A1 and EP 0 937736 A2, di- or polyfunctional alcohols, as described in DE 33 14 019 A1,DE 35 23 617 A1 and EP 0 450 922 A2, or β-hydroxyalkylamides, asdescribed in DE 102 04 938 A1 and U.S. Pat. No. 6,239,230.

Additionally described as suitable surface postcrosslinkers are alkylenecarbonates in DE 40 20 780 C1, 2-oxazolidinone and derivatives thereof,such as 2-hydroxyethyl-2-oxazolidinone, in DE 198 07 502 A1, bis- andpoly-2-oxazolidinones in DE 198 07 992 C1, 2-oxotetrahydro-1,3-oxazineand derivatives thereof in DE 198 54 573 A1, N-acyl-2-oxazolidinones inDE 198 54 574 A1, cyclic ureas in DE 102 04 937 A1, bicyclic amidoacetals in DE 103 34 584 A1, oxetanes and cyclic ureas in EP 1 199 327A2 and morpholine-2,3-dione and derivatives thereof in WO 2003/031482A1.

In addition, it is also possible to use surface postcrosslinkers whichcomprise additional polymerizable ethylenically unsaturated groups, asdescribed in DE 37 13 601 A1.

In addition, it is possible to use any desired mixtures of the suitablesurface postcrosslinkers.

Preferred surface postcrosslinkers are alkylene carbonates,2-oxazolidinones, bis- and poly-2-oxazolidinones,2-oxotetrahydro-1,3-oxazines, N-acyl-2-oxazolidinones, cyclic ureas,bicyclic amido acetals, oxetanes, bisoxetanes and morpholine-2,3-diones.

Particularly preferred surface postcrosslinkers are ethylene carbonate(1,3-dioxolan-2-one), trimethylene carbonate (1,3-dioxan-2-one),3-methyl-3-oxethanemethanol, 2-hydroxyethyl-2-oxazolidinone,2-oxazolidinone and methyl-2-oxazolidinone.

Very particular preference is given to ethylene carbonate.

The amount of surface postcrosslinker is preferably 0.1% to 10% byweight, more preferably 0.5% to 7.5% by weight and most preferably 1% to5% by weight, based in each case on the polymer particles.

The surface postcrosslinkers are typically used in the form of anaqueous solution. The amount of the solvent is preferably 0.001 to 8% byweight, more preferably 2 to 7% by weight, even more preferably 3 to 6%by weight and especially 4 to 5% by weight, based in each case on thepolymer particles. The penetration depth of the surface postcrosslinkerinto the polymer particles can be adjusted via the content of nonaqueoussolvent and total amount of solvent.

When exclusively water is used as the solvent, a surfactant isadvantageously added. This improves the wetting characteristics andreduces the tendency to form lumps. However, preference is given tousing solvent mixtures, for example isopropanol/water,1,3-propanediol/water and propylene glycol/water, where the mixing ratioin terms of mass is preferably from 10:90 to 60:40.

In a preferred embodiment of the present invention, cations, especiallypolyvalent cations, are applied to the particle surface in addition tothe surface postcrosslinkers before, during or after the thermal surfacepostcrosslinking.

The polyvalent cations usable in the process according to the inventionare, for example, divalent cations such as the cations of zinc,magnesium, calcium, iron and strontium, trivalent cations such as thecations of aluminum, iron, chromium, rare earths and manganese,tetravalent cations such as the cations of titanium and zirconium.Possible counterions are hydroxide, chloride, bromide, sulfate,hydrogensulfate, carbonate, hydrogencarbonate, nitrate, phosphate,hydrogenphosphate, dihydrogenphosphate and carboxylate, such as acetate,citrate and lactate. Salts with different counterions are also possible,for example basic aluminum salts such as aluminum monoacetate oraluminum monolactate. Aluminum sulfate, aluminum monoacetate andaluminum lactate are preferred. Apart from metal salts, it is alsopossible to use polyamines as polyvalent cations.

The amount of polyvalent cation used is, for example, 0.001% to 1.5% byweight, preferably 0.005% to 1% by weight and more preferably 0.02% to0.8% by weight, based in each case on the polymer particles.

In a further preferred embodiment of the present invention,hydrophilizing agents are additionally applied before, during or afterthe thermal surface postcrosslinking, for example sugar alcohols such assorbitol, mannitol and xylitol, water-soluble polymers or copolymerssuch as cellulose, polyethylene glycols, polyvinyl alcohols,polyvinylpyrrolidones and polyacrylamides.

The surface postcrosslinking is typically performed in such a way that asolution of the surface postcrosslinker is sprayed onto the driedpolymer particles. After the spray application, the surfacepostcrosslinker-coated polymer particles are thermally surfacepostcrosslinked.

The spray application of a solution of the surface postcrosslinker ispreferably performed in mixers with moving mixing tools, such as screwmixers, disk mixers and paddle mixers. Particular preference is given tohorizontal mixers such as paddle mixers, very particular preference tovertical mixers. The distinction between horizontal mixers and verticalmixers is made by the position of the mixing shaft, i.e. horizontalmixers have a horizontally mounted mixing shaft and vertical mixers avertically mounted mixing shaft. Suitable mixers are, for example,horizontal Pflugschar® plowshare mixers (Gebr. Lödige Maschinenbau GmbH;Paderborn; Germany), Vrieco-Nauta continuous mixers (Hosokawa Micron BV;Doetinchem; the Netherlands), Processall Mixmill mixers (ProcessallIncorporated; Cincinnati; USA) and Schugi Flexomix® (Hosokawa Micron BV;Doetinchem; the Netherlands). However, it is also possible to spray onthe surface postcrosslinker solution in a fluidized bed.

The thermal surface postcrosslinking is preferably performed in contactdriers, more preferably paddle driers, most preferably disk driers.Suitable driers are, for example, Hosokawa Bepex® Horizontal PaddleDryers (Hosokawa Micron GmbH; Leingarten; Germany), Hosokawa Bepex® DiscDryers (Hosokawa Micron GmbH; Leingarten; Germany), Holo-Flite® driers(Metso Minerals Industries Inc.; Danville; USA) and Nara Paddle Dryers(NARA Machinery Europe; Frechen; Germany). Moreover, fluidized beddriers may also be used.

The thermal surface postcrosslinking can be effected in the mixeritself, by heating the jacket or blowing in warm air. Equally suitableis a downstream drier, for example a shelf drier, a rotary tube oven ora heatable screw. It is particularly advantageous to effect mixing andthermal surface postcrosslinking in a fluidized bed drier.

It may be advantageous to conduct the thermal surface postcrosslinkingunder reduced pressure or to conduct it with use of drying gases, forexample dried air and nitrogen, in order to ensure the very substantialremoval of the solvents.

Subsequently, the surface postcrosslinked polymer particles can beclassified, with removal of excessively small and/or excessively largepolymer particles and recycling thereof into the process.

The surface postcrosslinking can also be conducted in the polymerdispersion. For this purpose, the solution of the surfacepostcrosslinker is added to the polymer dispersion. In this context, itmay be advantageous to conduct the thermal surface postcrosslinkingunder elevated pressure, for example with use of hydrophobic organicsolvents having a boiling point at 1013 mbar below the desiredtemperature for the thermal surface postcrosslinking. After the thermalsurface postcrosslinking in the polymer dispersion, the water-absorbingpolymer particles are dewatered azeotropically in the polymer dispersionand removed from the polymer dispersion, and the water-absorbing polymerparticles removed are dried to remove the adhering residual hydrophobicsolvent.

Preferred surface postcrosslinking temperatures are in the range of 100to 190° C., preferably in the range of 105 to 180° C., more preferablyin the range of 110 to 175° C., most preferably in the range of 120 to170° C. The preferred residence time at this temperature is preferablyat least 10 minutes, more preferably at least 20 minutes, mostpreferably at least 30 minutes, and typically at most 120 minutes.

In a preferred embodiment of the present invention, the water-absorbingpolymer particles are cooled after the thermal surface postcrosslinkingin a contact drier. The cooling is preferably performed in contactcoolers, more preferably paddle coolers and most preferably diskcoolers. Suitable coolers are, for example, Hosokawa Bepex® HorizontalPaddle Cooler (Hosokawa Micron GmbH; Leingarten; Germany), HosokawaBepex® Disc Cooler (Hosokawa Micron GmbH; Leingarten; Germany),Holo-Flite® coolers (Metso Minerals Industries Inc.; Danville; USA) andNara Paddle Cooler (NARA Machinery Europe; Frechen; Germany). Moreover,fluidized bed coolers may also be used.

In the cooler, the water-absorbing polymer particles are cooled to 20 to150° C., preferably 30 to 120° C., more preferably 40 to 100° C. andmost preferably 50 to 80° C.

To further improve the properties, the polymer particles thermallysurface postcrosslinked in a contact drier can be coated orremoisturized.

The remoisturizing is preferably performed at 30 to 80° C., morepreferably at 35 to 70° C., most preferably at 40 to 60° C. Atexcessively low temperatures, the water-absorbing polymer particles tendto form lumps, and, at higher temperatures, water already evaporates toa noticeable degree. The amount of water used for remoisturizing ispreferably from 1 to 10% by weight, more preferably from 2 to 8% byweight and most preferably from 3 to 5% by weight. The remoisturizingincreases the mechanical stability of the polymer particles and reducestheir tendency to static charging.

Suitable coatings for improving the free swell rate and the permeability(SFC) are, for example, inorganic inert substances, such aswater-insoluble metal salts, organic polymers, cationic polymers and di-or polyvalent metal cations. Suitable coatings for dust binding are, forexample, polyols. Suitable coatings for counteracting the undesiredcaking tendency of the polymer particles are, for example, fumed silica,such as Aerosil® 200, and surfactants, such as Span® 20 and Plantacare818 UP and surfactant mixtures.

The present invention further provides the water-absorbing polymerparticles obtainable by the process according to the invention.

The water-absorbing polymer particles obtainable by the processaccording to the invention have a centrifuge retention capacity (CRC) ofat least 37 g/g, an absorption under a pressure of 21.0 g/cm² of atleast 30 g/g, an absorption under a pressure of 49.2 g/cm² (AUHL) of atleast 14 g/g, a sum total of centrifuge retention capacity andabsorption under a pressure of 21.0 g/cm² (CRC+AUL) of at least 69 g/g,a sum total of centrifuge retention capacity and absorption under apressure of 49.2 g/cm² (CRC+AUHL) of at least 54 g/g, and less than 20%by weight of extractables.

The inventive water-absorbing polymer particles have a centrifugeretention capacity (CRC) of preferably at least 38 g/g, more preferablyat least 40 g/g and most preferably at least 41 g/g. The centrifugeretention capacity (CRC) of the water-absorbing polymer particles istypically less than 75 g/g.

The inventive water-absorbing polymer particles have an absorption undera pressure of 21.0 g/cm² (AUL) of preferably at least 32 g/g, morepreferably at least 33 g/g and most preferably at least 34 g/g. Theabsorption under a pressure of 21.0 g/cm² (AUL) of the water-absorbingpolymer particles is typically less than 50 g/g.

The inventive water-absorbing polymer particles have an absorption undera pressure of 49.2 g/cm² (AUHL) of preferably at least 16 g/g, morepreferably at least 18 g/g and most preferably at least 20 g/g. Theabsorption under a pressure of 49.2 g/cm² (AUHL) of the water-absorbingpolymer particles is typically less than 35 g/g.

The sum total of centrifuge retention capacity (CRC) and absorptionunder a pressure of 21.0 g/cm² (AUL) of the inventive water-absorbingpolymer particles is preferably at least 71 g/g, more preferably atleast 73 g/g, most preferably at least 74 g/g.

The sum total of centrifuge retention capacity (CRC) and absorptionunder a pressure of 49.2 g/cm² (AUHL) of the inventive water-absorbingpolymer particles is preferably at least 56 g/g, more preferably atleast 58 g/g, most preferably at least 59 g/g.

The inventive water-absorbing polymer particles comprise preferably lessthan 17% by weight, more preferably less than 15% by weight and mostpreferably less than 14% by weight of extractables.

The inventive water-absorbing polymer particles have a proportion ofparticles having a particle size of 300 to 600 pm of preferably at least30% by weight, more preferably at least 40% by weight and mostpreferably at least 50% by weight.

The present invention further provides hygiene articles comprising

-   -   (A) an upper liquid-permeable layer,    -   (B) a lower liquid-impermeable layer,    -   (C) a liquid-absorbing storage layer between layer (A) and layer        (B), comprising from 0 to 30% by weight of a fibrous material        and from 70 to 100% by weight of water-absorbing polymer        particles obtainable by the process according to the invention,    -   (D) optionally an acquisition and distribution layer between        layer (A) and layer (C), comprising from 80 to 100% by weight of        a fibrous material and from 0 to 20% by weight of        water-absorbing polymer particles obtainable by the process        according to the invention,    -   (E) optionally a fabric layer directly above and/or beneath        layer (C) and    -   (F) further optional components.

The proportion of water-absorbing polymer particles obtainable by theprocess according to the invention in the liquid-absorbing storage layer(C) is preferably at least 75% by weight, more preferably at least 80%by weight, most preferably at least 90% by weight.

The mean sphericity of the water-absorbing polymer particles obtainableby the process according to the invention in the liquid-absorbingstorage layer (C) is preferably less than 0.84, more preferably lessthan 0.82, most preferably less than 0.80.

Water-absorbing polymer particles having relatively low sphericity areobtained by suspension polymerization when the polymer particles areagglomerated during or after the polymerization. In the inventivehygiene articles, agglomerated water-absorbing polymer particles areused.

The water-absorbing polymer particles are tested by means of the testmethods described below.

Methods:

The measurements should, unless stated otherwise, be conducted at anambient temperature of 23±2° C. and a relative air humidity of 50±10%.The water-absorbing polymers are mixed thoroughly before themeasurement.

Residual Monomers

The residual monomer content of the water-absorbing polymer particles isdetermined by EDANA recommended test method WSP No. 210.2-05 “ResidualMonomers”.

Moisture Content

The moisture content of the water-absorbing polymer particles isdetermined by EDANA recommended test method No. WSP 230.3 (11) “MassLoss Upon Heating”.

Centrifuge Retention Capacity

The centrifuge retention capacity (CRC) is determined by EDANArecommended test method No. WSP 241.3(11) “Fluid Retention Capacity inSaline, After Centrifugation”.

Absorption Under A Pressure of 0.0 g/cm²

The absorption under a pressure of 0.0 g/cm² (AUNL) is determinedanalogously to EDANA recommended test method No. WSP 242.3 (11)“Gravimetric Determination of Absorption Under Pressure”, except that apressure of 0.0 g/cm² (AULO.Opsi) is established instead of a pressureof 21.0 g/cm² (AUL0.3 psi).

Absorption Under A Pressure of 21.0 g/cm²

The absorption under a pressure of 21.0 g/cm² (AUL) of thewater-absorbing polymer particles is determined by EDANA recommendedtest method No. WSP 242.3 (11) “Gravimetric Determination of AbsorptionUnder Pressure”.

Absorption Under A Pressure of 49.2 g/cm²

The absorption under a pressure of 49.2 g/cm² (AUHL) is determinedanalogously to EDANA recommended test method No. WSP 242.3 (11)“Gravimetric Determination of Absorption Under Pressure”, except that apressure of 49.2 g/cm² (AUL0.7 psi) is established instead of a pressureof 21.0 g/cm² (AUL0.3 psi).

Bulk Density

The bulk density is determined by EDANA recommended test method No. WSP250.3 (11) “Gravimetric Determination of Density”.

Extractables

The content of extractables of the water-absorbing polymer particles isdetermined by EDANA recommended test method No. WSP 270.3 (11)“Extractable”. The extraction time is 16 hours.

Free Swell Rate

To determine the free swell rate (FSR), 1.00 g (=W1) of thewater-absorbing polymer particles is weighed into a 25 ml beaker anddistributed homogeneously over its base. Then 20 ml of a 0.9% by weightsodium chloride solution are metered into a second beaker by means of adispenser and the contents of this beaker are added rapidly to the firstand a stopwatch is started. As soon as the last drop of salt solutionhas been absorbed, which is recognized by the disappearance of thereflection on the liquid surface, the stopwatch is stopped. The exactamount of liquid which has been poured out of the second beaker andabsorbed by the polymer in the first beaker is determined accurately byreweighing the second beaker (=W2). The time interval required for theabsorption, which has been measured with the stopwatch, is designated ast. The disappearance of the last liquid droplet on the surface isdetermined as the time t.

The free swell rate (FSR) is calculated therefrom as follows:

FSR [g/g s]=W2/(W1xt)

If the moisture content of the water-absorbing polymer particles,however, is more than 3% by weight, the weight W1 should be corrected totake account of this moisture content.

Vortex Test

50.0 ml ±1.0 ml of a 0.9% by weight aqueous sodium chloride solution areintroduced into a 100 ml beaker which comprises a magnetic stirrer barof size 30 mm×6 mm. A magnetic stirrer is used to stir the sodiumchloride solution at 600 rpm. Then 2.000 g ±0.010 g of water-absorbingpolymer particles are added as rapidly as possible, and the time takenfor the stirrer vortex to disappear as a result of the absorption of thesodium chloride solution by the water-absorbing polymer particles ismeasured. When measuring this time, the entire contents of the beakermay still be rotating as a homogeneous gel mass, but the surface of thegelated sodium chloride solution must no longer exhibit any individualturbulences. The time taken is reported as the vortex.

EXAMPLES

Production of the base polymer:

Example 1

A 2 L flange vessel equipped with impeller stirrer and reflux condenserwas initially charged with 340.00 g of heptane and 0.92 g of sucrosestearate (Ryoto® Sugar Ester S-370, Mitsubishi Chemical Europe GmbH,Dusseldorf, Germany), and heated to 70° C. until the sucrose stearatehad dissolved fully.

A monomer solution (first metered addition), prepared from 73.40 g(1.019 mol) of acrylic acid, 61.20 g (0.765 mol) of 50% by weightaqueous sodium hydroxide solution, 109.5 g of water and 0.11 g (0.407mmol) of potassium peroxodisulfate, was then introduced into a feedvessel and purged with air. Immediately prior to the dropwise additionof the monomer solution, at a stirrer speed of 300 rpm, the solution wasinertized by means of introduction of nitrogen and an oil bathtemperature of 55° C. was established.

After feeding had ended, the mixture was stirred at 70° C. for a furtherhour, then the reaction solution was cooled to about 25° C. and anice-cooled monomer solution (second metered addition), prepared from95.90 g (1.331 mol) of acrylic acid, 79.30 g (0.991 mol) of 50% byweight aqueous sodium hydroxide solution, 143.10 g of water and 0.14 g(0.518 mmol) of potassium peroxodisulfate, was introduced into a feedvessel and purged with air. Immediately prior to the dropwise additionof the monomer solution, at a stirrer speed of 300 rpm, the solution wasinertized by means of introduction of nitrogen. The monomer solution wasadded dropwise within 15 minutes.

After the feeding had ended, an oil bath temperature of 70° C. wasestablished. 120 minutes after commencement of heating, the refluxcondenser was exchanged for a water separator and water was separatedout.

The suspension present was cooled to 60° C. and the resultant polymerparticles were filtered off with suction using a Büchner funnel with apaper filter. The further drying was effected at 45° C. in an aircirculation drying cabinet and optionally in a vacuum drying cabinet at800 mbar down to a residual moisture content of less than 15% by weight.

The properties of the resulting polymer particles are summarized intable 2.

Examples 2 and 3

The base polymer was produced analogously to example 1 with the amountsstated in table 1. The properties of the resulting polymer particles aresummarized in table 2.

Example 4

The base polymer was produced analogously to example 1 with the amountsstated in table 1, and the first monomer solution (first meteredaddition) additionally comprised 3.0 g of 2-propanol (isopropanol).

The properties of the resulting polymer particles are summarized intable 2.

Example 5

A 2 L flange vessel equipped with impeller stirrer and reflux condenserwas initially charged with 896.00 g of cyclohexane, 2.00 g of Span® 20(sorbitan monolaurate), 3.20 g of Tixogel® VZ (organophilic bentonite)and 20.0 g of a 0.015% aqueous ascorbic acid solution, and heated tointernal temperature 75° C. while stirring and with introduction ofnitrogen.

A monomer solution, prepared from 150.00 g (2.082 mol) of acrylic acid,125.10 g (1.613 mol) of 50% by weight aqueous sodium hydroxide solution,138 g of water, 0.0375 g (0.243 mmol) of N,N′-methylenebisacrylamide(MBA) and 0.5 g (1.850 mmol) of potassium peroxodisulfate, was thenintroduced into a feed vessel and purged with air. Immediately prior tothe dropwise addition of the monomer solution, at a stirrer speed of 300rpm, the solution was inertized by means of introduction of nitrogen.Over the entire period over which the monomers were metered in, thereflux conditions were maintained. The monomer solution was addeddropwise within 60 minutes.

The end of feeding was followed by a further reaction time of 60minutes. Subsequently, the reflux condenser was exchanged for a waterseparator and water was separated out.

The suspension present was cooled to 60° C. and the resultant polymerparticles were filtered off with suction using a Büchner funnel with apaper filter. The further drying was effected at 45° C. in an aircirculation drying cabinet and optionally in a vacuum drying cabinet at800 mbar down to a residual moisture content of less than 15% by weight.

The properties of the resulting polymer particles are summarized intable 2.

Example 6

A 2 L flange vessel equipped with impeller stirrer and reflux condenserwas initially charged with 896.00 g of cyclohexane, 2.00 g of Span® 20(sorbitan monolaurate), 3.20 g of Tixogel® VZ (organophilic bentonite)and 20.0 g of a 0.015% aqueous ascorbic acid solution, and heated tointernal temperature 75° C. while stirring and with introduction ofnitrogen.

A monomer solution, prepared from 150.00 g (2.082 mol) of acrylic acid,118.0 g (1.475 mol) of 50% by weight aqueous sodium hydroxide solution,136.8 g of water, 0.075 g (0.194 mmol) of the triacrylate of 3-tuplyethoxylated glycerol (Gly-(EO-AA)₃) and 0.5 g (1.850 mmol) of potassiumperoxodisulfate, was then introduced into a feed vessel and purged withair. Immediately prior to the dropwise addition of the monomer solution,at a stirrer speed of 300 rpm, the solution was inertized by means ofintroduction of nitrogen. Over the entire period over which the monomerswere metered in, the reflux conditions were maintained. The monomersolution was added dropwise within 60 minutes.

The end of feeding was followed by a further reaction time of 60minutes. Subsequently, the reflux condenser was exchanged for a waterseparator and water was separated out.

The suspension present was cooled to 60° C. and the resultant polymerparticles were filtered off with suction using a Büchner funnel with apaper filter. The further drying was effected at 45° C. in an aircirculation drying cabinet and optionally in a vacuum drying cabinet at800 mbar down to a residual moisture content of less than 15% by weight.

The properties of the resulting polymer particles are summarized intable 2.

TABLE 1 Amounts of crosslinker b) used Step/ ppm mmol % Ex. feedCrosslinker b) g mmol boaa boaa 1 1 MBA 0 0 0 0 2 MBA 0 0 0 0 2 1 MBA0.009 0.06 125 6 2 MBA 0.012 0.08 125 6 3 1 MBA 0.018 0.12 250 12 2 MBA0.023 0.15 250 12 4 1 MBA*) 0.018 0.12 250 12 2 MBA*) 0.023 0.15 250 125 — MBA**) 0.0375 0.24 250 12 6 — Gly-(EO-AA)₃**) 0.075 0.19 500 9*)isopropanol as additional chain transfer reagent **)one-stage meteringboaa: based on (unneutralized) acrylic acid MBA: methylenebisacrylamideGly-(EO-AA)₃ triacrylate of 3-tuply ethoxylated glycerol

TABLE 2 Properties of the water-absorbing polymer particles (basepolymer) Bulk Moisture Extract- CRC AUNL AUL AUHL density content ablesEx. g/g g/g g/g g/g g/100 ml % % 1 55.0 44.3 7.2 6.6 89 2.2 34 2 46.154.1 7.3 6.7 78 4.5 21 3 42.8 52.0 7.4 6.5 79 4.4 21 4 48.4 54.1 7.8 7.283 4.0 20 5 40.7 39.9 7.5 6.6 70 3.5 26 6 64.0 9.7 6.9 6.1 91 2.0 29

Thermal surface postcrosslinking:

Examples 1-1 and 1-2

20 g of base polymer from example 1 were introduced into a mixer of theWaring® 32BL80 (8011) blender type. Subsequently, the mixer was switchedon at level 1. Immediately thereafter, 1.5 g of an aqueous solutionconsisting of 0.5 g of ethylene carbonate and 1.0 g of water, accordingto table 3, were introduced into a pipette and metered into the mixerwithin 2 seconds. After 3 seconds, the mixer was switched off and theresultant polymer particles were distributed homogeneously in a glassdish having a diameter of 20 cm. For thermal surface postcrosslinking,the glass dish filled with the polymer particles was heated in an aircirculation drying cabinet at 160° C. for 60 or 120 minutes. The polymerparticles were transferred to a cold glass dish. Finally, the coarserparticles were removed with a sieve having a mesh size of 850 μm.

The properties of the polymer particles are summarized in table 4.

Examples 2-1 and 2-2

The thermal surface postcrosslinking was effected analogously to example1-1 and 1-2, except using the base polymer from example 2. Thetemperature in the air circulation drying cabinet was 160° C. The heattreatment time was 60 or 120 minutes. The conditions are summarized intable 3.

The properties of the polymer particles are summarized in table 4.

Examples 3-1 and 3-2

The thermal surface postcrosslinking was effected analogously to example1-1 and 1-2, except using the base polymer from example 3. Thetemperature in the air circulation drying cabinet was 160° C. The heattreatment time was 60 or 120 minutes. The conditions are summarized intable 3.

The properties of the polymer particles are summarized in table 4.

Examples 3-3 and 3-4

The thermal surface postcrosslinking was effected analogously to example1-1, except using the base polymer from example 3 and usingN,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (Primid® XL 552) assurface postcrosslinker. The temperature in the air circulation dryingcabinet was 160° C. The heat treatment time was 60 minutes. Theconditions are summarized in table 3.

The properties of the polymer particles are summarized in table 4.

Examples 3-5 and 3-6

The thermal surface postcrosslinking was effected analogously to example1-1, except using the base polymer from example 3. The temperature inthe air circulation drying cabinet was 90° C. or 200° C. The heattreatment time was 60 minutes. The conditions are summarized in table 3.

The properties of the polymer particles are summarized in table 4.

Examples 4-1 and 4-2

The thermal surface postcrosslinking was effected analogously to example1-1 and 1-2, except using the base polymer from example 4. Thetemperature in the air circulation drying cabinet was 160° C. The heattreatment time was 60 or 120 minutes. The conditions are summarized intable 3.

The properties of the polymer particles are summarized in table 4.

Examples 5-1 and 5-2

The thermal surface postcrosslinking was effected analogously to example1-1 and 1-2, except using the base polymer from example 5. Thetemperature in the air circulation drying cabinet was 160° C. The heattreatment time was 60 or 120 minutes. The conditions are summarized intable 3.

The properties of the polymer particles are summarized in table 4.

Examples 6-1 and 6-2

The thermal surface postcrosslinking was effected analogously to example1-1 and 1-2, except using the base polymer from example 6. Thetemperature in the air circulation drying cabinet was 160° C. The heattreatment time was 60 or 120 minutes. The conditions are summarized intable 3.

The properties of the polymer particles are summarized in table 4.

Example 7

Example 1 from U.S. Pat. No. 8,003,210 was reworked.

The properties of the polymer particles are summarized in table 4.

TABLE 3 Thermal surface postcrosslinking in Waring ® blender -conditions Ethylene Ethylene carbonate Primid ® XL 552 Temperature Timecarbonate mmol per 20 Water Primid ® XL 552 mmol per 20 Ex. Crosslinkerb) ° C. min % by wt. bop g of polymer % by wt. bop % by wt. bop g ofpolymer 1  0 ppm MBA — — — — — — — 1-1 160 60 2.5 5.68 5 — — 1-2 160120  2.5 5.68 5 — — 2 125 ppm MBA — — — — — — — 2-1 160 60 2.5 5.68 5 —— 2-2 160 120  2.5 5.68 5 — — 3 250 ppm MBA — — — — — — — 3-1 160 60 2.55.68 5 — — 3-2 160 120  2.5 5.68 5 — — 3-3 160 60 — — 5 4.55 2.84 3-4160 60 — — 5 9.05 5.68 3-5  90 60 2.5 5.68 5 3-6 200 60 2.5 5.68 5 — — 4250 ppm MBA*) — — — — — — — 4-1 160 60 2.5 5.68 5 — — 4-2 160 120  2.55.68 5 — — 5 250 ppm MBA**) — — — — — — — 5-1 160 60 2.5 5.68 5 — — 5-2160 120  2.5 5.68 5 — — 6 500 ppm — — — — — — 6-1 Gly-(EO-AA)₃**) 160 602.5 5.68 5 — — 6-2 160 120  2.5 5.68 5 — — bop: based on (base) polymer*)isopropanol as additional chain transfer reagent **)one-stageagglomeration

TABLE 4 Thermal surface postcrosslinking in Waring ® blender -properties of the polymer particles CRC AUNL AUL AUHL Moisture contentExtractables Vortex FSR CRC + AUL CRC + AUHL Ex. g/g g/g g/g g/g % bywt. % by wt. s g/g s g/g g/g 1 55.0 44.3 7.2 6.6 2.2 34 200 0.06 62.261.6 1-1 46.0 59.0 26.0 9.3 1.2 5 194 0.08 72.0 55.3 1-2 43.8 55.5 34.019.7 1.1 13 192 0.12 77.8 63.5 2 46.1 54.1 7.32 6.7 4.5 21 96 0.27 53.452.79 2-1 37.5 63.8 32.9 10.7 0.6 6 100 0.19 70.4 48.2 2-2 37.5 60.438.7 24.3 0.8 4 95 0.15 76.2 61.8 3 42.8 52.0 7.4 6.5 4.4 21 70 0.2850.2 49.3 3-1 38.8 61.1 36.4 17.8 1.2 17 85 0.12 75.2 56.6 3-2 34.0 61.932.9 18.1 1.1 8 91 0.15 66.9 52.1 3-3 30.4 50.0 22.5 15.1 0.8 18 50 0.3452.9 45.5 3-4 29.1 42.6 22.4 14.9 1.2 21 75 0.30 51.5 43.9    3-5*) 41.952.6 7.6 7.1 2.9 22 71 0.26 49.5 49.0    3-6*) 29.0 49.2 26.2 14.2 1.321 76 0.33 55.2 43.2 4 48.4 54.1 7.8 7.2 4.0 20 130 0.13 56.2 55.6 4-145.0 62.3 37.5 14.4 1.7 3 120 0.07 82.5 59.4 4-2 42.8 60.2 39.3 26.2 1.23 127 0.10 82.1 69.0 5 40.7 39.3 7.5 6.6 3.5 26 60 0.09 48.2 47.3 5-140.1 53.7 18.8 7.2 2.4 16.1 50 0.14 58.9 47.3 5-2 37.8 55.3 33.0 16.30.9 11.2 49 0.18 70.8 54.1 6 64.0 9.7 6.9 6.1 2 29 92 0.18 70.9 70.1 6-145.2 53.0 26.9 12.1 1.1 18.3 90 0.13 72.1 57.3 6-2 40.5 56.6 30.3 16.30.9 12.0 90 0.11 70.8 56.8    7*) 44.3 63.9 12.1 7.1 4.0 22 62 0.33 56.451.4 *)comparative example

1. A process for producing water-absorbing polymer particles bypolymerizing a monomer solution comprising a) at least one ethylenicallyunsaturated monomer which bears an acid group and optionally is at leastpartly neutralized, b) optionally one or more crosslinker, c) at leastone initiator, d) optionally one or more ethylenically unsaturatedmonomer copolymerizable with the monomer mentioned under a), and e)optionally one or more water-soluble polymer, the monomer solutionsuspended in a hydrophobic organic solvent during the polymerizationbeing agglomerated during or after the polymerization in the hydrophobicorganic solvent, and thermally surface postcrosslinking the resultantagglomerated polymer particles by means of an organic surfacepostcrosslinker, wherein the amount of crosslinker b) is selected suchthat the agglomerated polymer particles before the surfacepostcrosslinking have a centrifuge retention capacity of at least 37 g/gand the thermal surface postcrosslinking is conducted at 100 to 190° C.2. The process according to claim 1, wherein agglomeration is effectedin the hydrophobic organic solvent after the polymerization.
 3. Theprocess according to claim 1, wherein the polymerization is conducted inthe presence of a chain transfer reagent.
 4. The process according toclaim 1, wherein the amount of crosslinker b) is selected such that thepolymer particles before the surface postcrosslinking have a centrifugeretention capacity of at least 40 g/g.
 5. The process according to claim1, wherein the thermal surface postcrosslinking is conducted at 120 to170° C.
 6. The process according to claim 1, wherein the organic surfacepostcrosslinker is selected from the group consisting of alkylenecarbonates, 2-oxazolidinones, bis- and poly-2-oxazolidinones,2-oxotetrahydro-1,3-oxazines, N-acyl-2-oxazolidinones, cyclic ureas,bicyclic amido acetals, oxetanes, and morpholine-2,3-diones.
 7. Theprocess according to claim 1, wherein from 1 to 5% by weight of organicsurface postcrosslinker is used, based on the resultant polymerparticles.
 8. The process according to claim 1, wherein at least onedispersing aid is used in the polymerization.
 9. The process accordingto claim 1, wherein the resultant polymer particles are at least partlydewatered azeotropically after the polymerization.
 10. The processaccording to claim 9, wherein the resultant polymer particles arefiltered and dried after the azeotropic dewatering.
 11. The processaccording to claim 1, wherein the thermal surface postcrosslinking isconducted in a mixer with moving mixing tools.
 12. Water-absorbingpolymer particles by a process of claim 1, having a centrifuge retentioncapacity of at least 37 g/g, an absorption under a pressure of 21.0g/cm² of at least 30 g/g, an absorption under a pressure of 49.2 g/cm²of at least 14 g/g, a sum total of centrifuge retention capacity andabsorption under a pressure of 21.0 g/cm² of at least 69 g/g, a sumtotal of centrifuge retention capacity and absorption under a pressureof 49.2 g/cm² of at least 54 g/g, and less than 20% by weight ofextractables.
 13. Water-absorbing polymer particles according to claim12, having a centrifuge retention capacity of at least 41 g/g. 14.Water-absorbing polymer particles according to claim 12, having anabsorption under a pressure of 21.0 g/cm² of at least 34 g/g. 15.Water-absorbing polymer particles according to claim 12, having anabsorption under a pressure of 49.2 g/cm² of at least 20 g/g. 16.Water-absorbing polymer particles according to claim 12, having a sumtotal of centrifuge retention capacity and absorption under a pressureof 21.0 g/cm² of at least 74 g/g.
 17. Water-absorbing polymer particlesaccording to claim 12, having a sum total of centrifuge retentioncapacity and absorption under a pressure of 49.2 g/cm² of at least 59g/g.
 18. Water-absorbing polymer particles according to claim 12, havingless than 14% by weight of extractables.
 19. Water-absorbing polymerparticles according to claim 12, having a bulk density of less than 1.0g/cm³.
 20. Water-absorbing polymer particles according to claim 12,wherein the proportion of particles having a particle size of 300 to 600μm is at least 30% by weight.
 21. A hygiene article comprising (A) anupper liquid-permeable layer, (B) a lower liquid-impermeable layer, (C)a liquid-absorbing storage layer between layer (A) and layer (B),comprising from 0% to 30% by weight of a fibrous material and from 70 to100% by weight of water-absorbing polymer particles according to, (D)optionally an acquisition and distribution layer between layer (A) andlayer (C), comprising from 80% to 100% by weight of a fibrous materialand from 0 to 20% by weight of water-absorbing polymer particlesaccording to, (E) optionally a fabric layer directly above and/orbeneath layer (C) and (F) further optional components, wherein thewater-absorbing polymer particles in (C) and (D) have a centrifugeretention capacity of at least 37 q/q, an absorption under a pressure of21.0 g/cm² of at least 30 g/g, an absorption under a pressure of 49.2g/cm² of at least 14 g/g, a sum total of centrifuge retention capacityand absorption under a pressure of 21.0 g/cm² of at least 69 g/g, a sumtotal of centrifuge retention capacity and absorption under a pressureof 49.2 g/cm² of at least 54 g/g, and less than 20% by weight ofextractables.